Process for the preparation of humous colloids



Patented June 20,1933 i 1,914,824

I UNITED. STATES PTENT. oFFIca RUDOLF EZBERHARD, OF MUNICH, G

PROCESS FOR PREPARATION OF HUMOUS COLLOIDS No Drawing. Application filedMay 6, 1929, Serial No. 860,999,'and in Germany May 22, 1928.

Methods are known for the preparation while preventing burning orotherwise damof water-soluble humous colloids from hu aging plants as isso frequently done by mous materials by treatment with waterstronglyalkaline media. In therapy, the soluble substances of an inorganiccharacter almost neutral reaction of the blood is not which exhibiteither acid or strongly basic disturbed by the resorption of suchneutral properties. Among the water-soluble subhumous colloids and withrespect to the stances having strongly basic properties, fermentativeprocesses of the glandular seused in existing methods, are causticalkalis cretions, in the dissociation of the nuclei and alkalis ofcarbonic and phosphoric acid. acids the said weakly alkaline humous col-10 Methods are also known in which, in lieu of loids in connection withtheir reducing propthe said strongly inorganic bases, use is made ertieseffect a retardation or prevention of of water soluble strongly basiccompounds oxidizing actions. The said colloids are of organic origin,such as pyridine or its waalso adapted for injections and for externalter soluble derivatives and compounds as therapeutic uses.

5 well as corresponding compounds of chino- Their preparation is thepurpose of the lin. The nature or composition of the dispresent process;Essentially it consists in solved humous compounds is dependent onallowing humous material of any kind and the character of said stronglybasic comorigin to react'with water-soluble nitrogenpounds; for example,by heating humous macontaining organic compounds. derivable 20 terialwith strong bases the originallyv exfrom ammonia of neutral or weaklyalkaisting labile amido compounds are decomline reaction under pressureor not, at ordiposed.' The preservation of these is hownary or raisedtemperature. By this means ever of considerable importance for variousthe disadvantages of the previously considpurposes, medicinal inparticular. ered methods are avoided, i. e., decomposi- The use ofpyridine and the llke has the tion or transformation of the volatile andadditional disadvanta e that it cannot be labile constituents of thehumous comcompletely removed cm the solution of pounds, (nitro en amidocompounds for exhumous substances and in view of the obample) iseliminated, in contrast to the corjectionable odor of pyridine itsresence, responding action of strongly alkaline subparticularly inmedicinal compoun is exstances of an inorganic or organic nature.tremely undesirable. The product of my process may be used Of hewater-soluble orgam Substances therapeutically .for all inflammatorycondi- Whi h can he d for P P t of tions in which resorptive efl'ect issought, for water-soluble humous colloids the socalled xa in the c f ifl ti f the indifferent Qx agents be joints, arthritic and rheumaticafiections,

y consldel'ed from a techmcal Stand parametritis, perimetritis, etc.

Roint since ,accprdjng the i in The diflerence between the chemicalcomhterature, the yields obtained w1t t cm are position of the reactionproducts of the i g gg fi ggfg fi ggz i gg g g gx gh humous substancesproduced by the neutral are however of greater importance for techorweakly alkahne methqd and nical and medicinal purposes. duced y hStrongly haslc methQd 1 also For technical purposes, these water sol-Shown by the fact that the Sohlhohs P uble humous colloids areadvantageously usdhchd by f Ph h d, after complete able in photographyfor the production of condehsatlfim and hardehlhg, P y al certain kindsof plates and films; for agrior crystalline powder which may ag incultural purposes the neutral or weakly al.- cornpletely dissolved inwater, as 'd t kaline nature of such colloids is important guished fromwhat may be done mth th in spraying plants for combatin the deactionproducts obtained by the strongly structive action of bugs, beetles anthe like, baslc procedure. The dissolving capacity of these products isof very great importance in many cases. 7 v

With the present process the aqueous solutions ofhexamethylenetetramine, urea, as indeed any water-solublenitrogen-containin derivatives of ammonia, homologues and su stitutio'nproducts of carbonic acid, formanilide, formaldoxime, acetaldehydeammonia and piperazine among others can be employed. These substancescan be employed of course alone or in mixtures.

The amides of the monobasic fatty-acids, acetamide or vformamideforexample, which are particularly suited to theextraction of drugs,cannot be included among the watersoluble nitrogen-containing compoundsof neutral reaction since they give no yield for all practical purposeswith humous material even on heating to boiling'for several hours.

As opposed to all prev1ousl know methods well-crystallized organic odiescan by the present process be obtained as products of reaction, e. g. bythe action of urea, bi-..

can be made to act in the molten state onhumous material.

According to the'new process for example 2 parts by weight of finelypowdered peat,

, 2 parts by weight of -formanilide and 20 arts by weight of waterareheated to 90 5. for an hour. The product is diluted with hot water,the deep brown solution obtained is separated from the residue' andconcentrated as desired.

Or: 4 arts by wei ht of urea,'4 parts by weight 0? finely pow ered peatand 40 arts by weight of water are heated to 95 pfor 2 hours. Theresulting deep brown solution is separated by pressing and afterfiltration can be made to yield crystals. Brown crystals are obtainedwhich dissolve in water to acolloidal solution of neutral reaction anddark brown colour.

To obtain combined humous colloids the reaction products obtained by theprevious method can be coupled with such organicand inorganic compounds,which are water-soluble or which dissolve in the aqueous solutions ofthe organic compounds mentioned as employed for the decomposition ofhumous material. Chemical substances which have reducing properties areespecially suitable. .Among others, e. g., can be employed water-solublealdehydes and their watersoluble derivatives, hydroquinone, resorcinol,pyrogallol, yeast, size, tannln and silver n1- trate, arsenic acid,mercuric chloride.

For example, 1 part by wei ht resorcinol is mixed with 2' parts by weigt formanilidehumate. The substance which separates outwill dissolve onaddition of. three parts by weight of water and warming to a greybrownliquid of alkaline reaction which opalesces on dilution.

Or: 5 parts by weight of-the described urea humate crystals aredissolved in 20 parts by weight of water and to this solution is added 1part of silver nitrate.

clear brown li uid of neutral reaction is obtained. That t e silver ishere bound to the humate can be readily proved, e. g.,. silver mirrorafter precipitation with hydrochloric "acid.

The humous colloids obtained by the newly-discovered process can also becombined with such organic or inorganic compounds as dissolve in themelts of the nitrogencontaining organic compounds emplo ed for thepreparation of the starting pro ucts or in their mixed melts. Thefollowing can be employed, e. g.; chlorophyll, aniline, iodine, hydratedsilicic acid, calcium fluoride, aluminium hydroxide, mercury sulphide,etc.

For example: 5parts by weight urea are I heated until fused and in themelt 0,5 parts by weight chlorophyll and 0,3 parts b weight aluminiumhydroxide are introduce The melt is heated for a further time until gasis evolved and the thickish hot mass is dissolved in 20 parts by weightof the described formanilide humate.

A modification of the present processis the use-of water-solublenitrogen-containing organic compounds of neutral or weakly alkalinereaction which contain sulphur in addition to the above mentionednitrogenous groups for obtaining sulphur-containing humous colloids.Tothis end can be used thiourea, ammonium thiocyanate etc.

For example: 10 parts by weight thiourea and parts by weight sodiumthiosul hate are dissolved in 50 parts by weight 0 water, mixed with 15parts by weight of peat and heated to C. for 2 hours. After separationby pressing and thickening a yelcan be added either to the prepared.humous collolds or to the starting substances or durmg the preparation.

f the sulphur-free humous colloids obtamed by the present process, e.g., the neutral formanihde humate, are treated with acids, 0. g.phosphoric acid, only a part of the humic acids separates slowly whilethe remaining part remains dissolved with-a ruby-red colour. Thesehumins in acid 50- lution can likewise be cou led with theaforementioned combining 'es.

. I claim:

1. The herein described process of pro ducinghumous colloids of neutralcharacter, which consists in reacting 'peatwith water soluble organiccompounds of neutral reac- 1 tion containing nitrogen groups derivablefrom ammonia.

2. The herein described process of producing humous colloids of neutralcharacter, which consists in reacting peat with water soluble organiccompounds of neutral reaction contaming nitrogen grou s derivable fromammonia; said reaction effected in the presence of iodine.

' 3. The herein described. process of producing humous colloidsofneutral character, which consists in reacting peat with water solubleorganic sulphur-containing compounds of neutral reaction containingnitrogen groups derivable from ammonia.

4. The herein described process of producing humous colloids of neutralcharacter,v comprising the step of claim 2 and the additional step ofeifecting crystallization of the reaction products. 7 5. The hereindescribed process of producing humous colloids of neutral character,comprising the step of claim 2 and the additional step of adding acid tothe reaction product to obtain a final product in acid solution. 7

In testimony whereof I hereunto afiix my signature.

. V RUDOLF- EBERHARD.

